a green process for niacinamide production
TRANSCRIPT
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University of Pennsylvania
ScholarlyCommons
Senior Design Reports (CBE)Department of Chemical & Biomolecular
Engineering
4-1-2013
A Green Process for Niacinamide ProductionPraveen BainsUniversity of Pennsylvania
Ashley Clark University of Pennsylvania
Amber Lowey University of Pennsylvania
Jamie SooUniversity of Pennsylvania
http://repository.upenn.edu/http://repository.upenn.edu/cbe_sdrhttp://repository.upenn.edu/cbehttp://repository.upenn.edu/cbehttp://repository.upenn.edu/cbehttp://repository.upenn.edu/cbehttp://repository.upenn.edu/cbe_sdrhttp://repository.upenn.edu/
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A Green Process for Niacinamide Production
Abstract
Tis project proposes a plant in which niacinamide can be produced with an environmentally green process.Specically, it takes 2-methyl-1,5-pentanediamine (MPDA) as a starting reactant and converts it to picoline before subsequently converting it to niacinamide and purifying the nal product. By following this particularreaction path, the process avoids the more classic method of preparation by which nicotine is oxidized withpotassium dichromate, a reaction with considerably more toxic reactants and waste. Along with this moresustainable reaction path, care was taken to ensure the process was as green as possible at each step along the
way.
Te primary global supplier of niacin is Lonza, whose patent provided the base upon which this process wasdeveloped. Only preliminary data was furnished by the patent; the majority of the process presented withinthis portfolio was developed with limited information from the patent reference.
Te base-case process presented in this project consists of three main sections; Block 100 involves theconversion of MPDA into picoline, Block 200 involves the formation of niacinamide from picoline, and Block 300 involves the separation and purication of the niacinamide into the nal marketable product. A nalpurity of 97.7% by weight was achieved. Rigorous economic analysis was performed on the entirety of theprocess, yielding an NPV of $4,932,800 aer 20 years and an internal rate of return (IRR) of 16.82% aer thethird year. Although each of these indicate a positive return on investment, as the economic success of thisprocess is highly subject to the market value of both the feedstock MPDA and product niacinamide, furtherinvestigation may be necessary before nal project approval.
Disciplines
Biochemical and Biomolecular Engineering | Chemical Engineering | Engineering
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A GREEN PROCESS FOR
NIACINAMIDE PRODUCTION
Praveen Bains
Ashley Clark
Amber Lowey
Jamie Soo
U i i f P l i
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University of Pennsylvania
School of Engineering and Applied ScienceDepartment of Chemical and Biomolecular Engineering220 South 33rd StreetPhiladelphia, PA 19104
April 9, 2013
Dear Mr. Fabiano and Dr. Holleran,
Enclosed is our proposed process design for the green production of niacinamide from an
environmentally friendly facility, as specified in a problem statement by Mr. Fabiano. Our plant
design entails two reaction sections and a separation train to obtain 97.7% by weight final product
purity. We have also designed a Dowtherm distribution system to help achieve our heating
requirements throughout the system.
Our finalized process includes three distinct sections. In the first, 2-methyl-1,5-
pentanediamine is converted to 3-picoline, in the second section 3-picoline is converted to the desired
product niacinamide, and the third separates and purifies the final product. By utilizing the raw
material of 2-methyl-1,5-pentanediamine, this process is able to avoid the formation of harsh
intermediates like acrolein and is significantly more sustainable and environmentally conscientious
than previous niacin production processes.
The following report details the specifics of the process, the equipment needs for each stage
of the process, the estimated costs and power requirements of each piece of equipment, and a detailed
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Table of Contents Bains, Clark, Lowey, Soo
Table of Contents I. ABSTRACT ............................................................................................................................................. 1
II. I NTRODUCTION AND PROJECT CHARTER .............................................................................................. 3
A. PROJECT CHARTER ........................................................................................................................... 4
B. PROJECT MOTIVATION ..................................................................................................................... 5
C. METHODS OF PRODUCTION .............................................................................................................. 7
Raw Materials ....................................................................................................................................... 7
Reaction ................................................................................................................................................ 8
Sustainability ......................................................................................................................................... 9
Plant Location ..................................................................................................................................... 10
Plant Capacity ..................................................................................................................................... 10
III. I NNOVATION MAP .......................................................................................................................... 11
IV. CONCEPT STAGE ............................................................................................................................ 13
A. MARKET AND COMPETITIVE A NALYSIS ......................................................................................... 14
V. PROCESS DESIGN ................................................................................................................................. 17
A. PROCESS FLOW DIAGRAM AND MATERIAL BALANCES ................................................................. 18
Block (100) ........................................................................................................................................ 19
Block (200) ......................................................................................................................................... 21
Block (300) ......................................................................................................................................... 25
B. PROCESS DESCRIPTION .................................................................................................................. 27
Block (100): Reaction Train 1 — MPDA to PIC .................................................................................. 27
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Table of Contents Bains, Clark, Lowey, Soo
Startup Considerations ...................................................................................................................... 120
Purity Improvement .......................................................................................................................... 121
Schedule ............................................................................................................................................ 122
Miscellaneous ................................................................................................................................... 122
H. E NERGY BALANCE AND UTILITY R EQUIREMENTS ...................................................................... 123
Energy Balance ................................................................................................................................. 123
Utility Requirements ......................................................................................................................... 125
I. OPERATING COST AND ECONOMIC A NALYSIS ............................................................................. 131
Operating Cost Summary .................................................................................................................. 132
Cash Flow and Profitability Analysis ............................................................................................... 135
J. SENSITIVITY ANALYSES ............................................................................................................... 137
Product Price and Variable Costs ...................................................................................................... 137
Feedstock Price ................................................................................................................................. 139
Inflation Rate .................................................................................................................................... 140
MPDA to Niacinamide Ratio ............................................................................................................ 140
VI. CONCLUSIONS AND R ECOMMENDATIONS .................................................................................... 143
VII. ACKNOWLEDGMENTS .................................................................................................................. 147
VIII. R EFERENCES ................................................................................................................................ 149
IX. APPENDIX ..................................................................................................................................... 159
A. PROBLEM STATEMENT ................................................................................................................. 160
B. R ELEVANT PATENTS .................................................................................................................... 162
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Table of Contents Bains, Clark, Lowey, Soo
Sample Blower Calculations (B-101) ............................................................................................... 247
Sample Compressor Calculations (C-101) ........................................................................................ 248
Sample Vapor Liquid Separator Calculations ................................................................................... 249
Sample Heat Exchanger Calculations ............................................................................................... 250
Sample Vertical Pressure Vessel Calculations .................................................................................. 251
Sample Pump Calculations ............................................................................................................... 252
Sample Reactor Calculations (R-202A, B, C) .................................................................................. 253
Sample Storage Vessel Calculations (T-101) ................................................................................... 254
E. PROFITABILITY A NALYSIS SPREADSHEET ................................................................................... 256
F. MSDS AND COMPOUND DATA .................................................................................................... 262
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I.
ABSTRACT
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Table of Contents Bains, Clark, Lowey, Soo
A.
ABSTRACT
This project proposes a plant in which niacinamide can be produced with an environmentally green
process. Specifically, it takes 2-methyl-1,5-pentanediamine (MPDA) as a starting reactant and converts it
to picoline before subsequently converting it to niacinamide and purifying the final product. By following
this particular reaction path, the process avoids the more classic method of preparation by which nicotine
is oxidized with potassium dichromate, a reaction with considerably more toxic reactants and waste.
Along with this more sustainable reaction path, care was taken to ensure the process was as green as
possible at each step along the way.
The primary global supplier of niacin is Lonza, whose patent provided the base upon which this process
was developed. Only preliminary data was furnished by the patent; the majority of the process presented
within this portfolio was developed with limited information from the patent reference.
The base-case process presented in this project consists of three main sections; Block 100 involves the
conversion of MPDA into picoline, Block 200 involves the formation of niacinamide from picoline, and
Block 300 involves the separation and purification of the niacinamide into the final marketable product. A
final purity of 97.7% by weight was achieved. Rigorous economic analysis was performed on the entirety
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II.
INTRODUCTION AND
PROJECT CHARTER
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
A.
PROJECT CHARTER
Project Name A Green Process for Niacinamide Production
Project Champion Professor Leonard A. Fabiano, U. Penn
Project Advisor Dr. Sean P. Holleran, U. Penn
Project Leaders Praveen Bains, Ashley Clark, Amber Lowey, Jamie Soo
Specific Goals Design and determine the economic viability of a plant that produces competitiveamounts of niacinamide to capture an equivalent amount of market share ofniacinamide as the Lonza company
Project Scope In Scope
Determining the world market for niacin and the current worldwide production capacity
Determining the selling price of niacin
Developing a process design of a facility that produces 27.7 MM lbs/yrniacinamide based on the Lonza process
Building upon and fully realize the existing process flowsheet described inLonza’s patent
Completing approximate equipment sizing and costin g
Determining economic viability of the proposed facility
Producing niacinamide of at least 95 weight % purity
Out of Scope Verifying reaction kinetics, conversions, and yields proposed in the Lonza
patent
Developing wastewater treatment facilities, air scrubbing units, Dowthermheating systems, and refrigeration systems
Determining safety layout of facilities
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
B.
PROJECT MOTIVATION
This project has been commissioned to produce niacin on a scale capable of being competitive in the
world markets and of comparable market share as primary producers such as Lonza or Jubilant.
Additionally, this project is intended to explore various methods of reducing the environmental footprint
of the overall process and improving its general sustainability. Niacin is important as a supplement for
human consumption and as an additive to animal feed. Naturally, these markets have differing standards
of purity. The importance of niacin is further discussed in the Market and Competitive Analysis in section
IV Concept Stage.
The process that was developed was modeled on the Lonza process patent, a niacin production method
which utilizes picoline as an intermediate reactant known for its “green chemistry”. This additional step
allows the use of acrolein to be avoided, thereby reducing the amount of hazardous intermediates
involved. Aside from the reaction process itself, the Lonza process has also established a set of guidelines
which encompass nearly every factor of production from choice of feedstock to treatment of wastes,
aimed at minimizing the overall footprint of production.
Beyond the adoption of the use of picoline, the Lonza process takes many other green factors into account
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
costs and initial capital investment for a determined ideal production rate, the final profitability and return
on investment must be calculated.
The project aims to develop a process which improves the environmental impact of production and can
thus be simultaneously profitable and environmentally sustainable.
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
C.
METHODS OF PRODUCTION
Patent US5719045 from Lonza served as the basis for our process, providing the reaction pathway and
reactor conditions necessary for niacinamide production. A separation and purification process was then
designed to obtain the necessary purity for our targeted market of 95% for animal feed. The production
begins with a series of four reactor systems: two tubular reactors, one packed-bed reaction, and
continuously-stirred tank reactors (CSTRs) in series. The biocatalyst Rhodococcus rhodocrous is used in
the CSTRs. Hydrogen is separated after the second reactor for use as the Dowtherm system fuel. The
slurry product stream then undergoes a single distillation, two flash vaporizers, and concludes at a
nitrogen-fed dryer. The result is a final product stream of niacinamide with 97.7 weight % purity as a
powder. This is suitable for the animal feed market.
Raw Materials
The raw materials for the process include MPDA, water, oxygen, and nitrogen. The table below denotes
the cost of each of these. The cost of MPDA was estimated by dividing the cost of MPDA from Sigma
Aldrich by a factor of 10. This factor was determined by comparing bulk and non-bulk prices of other
chemicals, such as niacinamide.
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
Catalyst Total Price ($/)
HZSM-5 (Zeolite) $3,810
Pd-SiO2/Al2O3 $783,300V2O5/TiO2/ZrO2/MoO3 $1,646,000
Rhodococcus rhodocrous $153,900
Table C2. Prices of catalysts used in niacinamide production.
Reaction
The reaction pathway proposed by Lonza in the patent US5719045 was followed to produce niacinamide.
The Lonza method of niacin production follows two stages with two reactions in each. The first set
produces the starting material for niacin production, 3-picoline. The second set oxidizes the picoline to
form niacinamide and niacin.
The process begins with MPDA as the starting raw material, which is a byproduct of the nylon-6,6
industry. The liquid MPDA is first vaporized and is converted to 3-methylpiperidine (MPI) via
deamination, resulting in a ring closure. This exothermic reaction takes place in the presence of the zeolite
catalyst, HZSM-5:
[MPDA] [MPI] + [NH3] (1)
The methyl piperidine is then dehydrogenated endothermically to 3-picoline (PIC) over a Pd-SiO2/Al2O3
catalyst:
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
[CNP] + [H2O] [niacinamide] (5)
The yields of niacinamide are determined by adjusting the pH of the fourth reactor, which consists of
three CSTRs in series. The products then travel through a separation train to form a high purity, powdered
form.
An overview of the reaction steps are shown below, reproduced from a paper written by Roderick Chuck
from Lonza.
Figure 1. Conversion of MPDA to MPI and MPI to PIC.
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II. Introduction and Project Charter Bains, Clark, Lowey, Soo
atmospheric pressure for each reaction, and recoverable energy from the exothermic reactions. While
building the niacinamide production process, careful attention was given to increasing its sustainability.
In the Lonza patent, the hydrogen gas was burned directly to evaporate the MPDA. In this project, the
hydrogen byproduct is separated and sent to fuel a Dowtherm heating system. Dowtherm A is used as a
heat transfer fluid that maintains the high temperatures required for the dehydrogenation reaction and
other heat exchangers. Wet scrubbers are used to remove the minimal CO2 released during the process.
Furthermore, the startup fuel chosen for the Dowtherm system is renewable natural gas, an upgraded
version of biogas, which releases less CO2 than natural gas. Renewable natural gas does not require
hydraulic fracturing as it is created from biomass. These aspects contribute to the overall sustainability of
the niacinamide production process. Additionally, water is the only solvent required, and toxic chemical
such as ammonia and Dowtherm A are recycled within the system.
Plant Location
The niacinamide production plant will be located in Michigan, due to its proximity to a producer of the
raw material MPDA, Invista. Invista owns a manufacturing plant in Mississauga, Ontario, just across the
lake. This will reduce cost of transportation greatly. The proximity of other chemical plants in the area
also indicates the availability of utilities for running a process plant. For distribution of the product, this
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III.
INNOVATION M AP
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III. Innovation Map Bains, Clark, Lowey, Soo
12
Eliminate reaction
from nicotine to
nicotinic acid
Reduce carbon
intermediates that
burn readily
Customer-
Value
Proposition
Starting material
from nylonmanufacturing
waste
Eliminate the need for
hazardous materials (e.g.
acrolein)
Niacin
Generate energy for use in
heating endothermic
reactor
Produce and store
niacin with limited
byproducts
Efficient burning of
H2 as a fuel in excess
oxygen
Hydrogen and oxygen
byproducts separated
via simple flash vessel
Products
Technical
Differentiation
Process/
ManufacturingTechnology
High chemical
compatibility with
compounds in
finished product
Bacteria
biocatalyst used inthe last reaction
step
Higher conversion
of intermediates
Reduce CO andCO2 production
during process
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IV. CONCEPT S TAGE
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IV. Concept Stage Bains, Clark, Lowey, Soo
A.
MARKET AND COMPETITIVE ANALYSIS
The term niacin is commonly used to describe both nicotinic acid and niacinamide. Both of these
compounds are water-soluble and are part of the vitamin B group. Nicotinic acid and niacinamide are
necessary for all living cells as they are essential contributors to proper carbohydrate, protein and lipid
metabolism.
Niacinamide and nicotinic acid are components of the coenzymes niacinamide dinucleotide (NAD) and
niacinamide adenine dinucleotide phosphate (NADP), which are both key intermediates in the metabolic
process. More than 40 biochemical reactions have been identified that utilize these coenzymes,
particularly in relation to the skin, gastrointestinal tract and nervous system. In humans, a deficiency of
niacin can result in a wide variety of symptoms, from severe digestive system disorders, to weakness, skin
discoloration, loss of appetite, and retarded growth.
Due to its great importance in biological functions, niacin is most commonly used in feed, food, and
pharmaceutical industries. The global market size of niacin and niacinamide is over $400 million USD,
with an estimated production rate of 20,200 metric ton per year (TPA) or 44,603,000 lbs/yr (Lonza Group,
Ltd., 2011). Its largest market demand is as a feed supplement feed for stock animals, accounting for 60-
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IV. Concept Stage Bains, Clark, Lowey, Soo
production with a production rate of 10,700 TPA (2,362,000 lbs/yr). Lonza controls three large-scale
plants, one operating in Switzerland where the firm is based and two others operating in China
(Pharmaceutical-Technology, 2011). Jubilant is based in India, and as of 2011, has a commercial
production rate of 10,000 TPA niacinamide per year.
The plant designed in this report will produce 3,452 lb/hr of niacinamide at 97.7% by weight purity,
targeting the animal nutrition industry as our primary consumer. This targeted output is intended to be
competitive with Lonza and Jubilant but will not flood the market.
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V.
PROCESS DESIGN
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V. Process Design Bains, Clark, Lowey, Soo
A.
PROCESS FLOW DIAGRAM AND MATERIAL BALANCES
Outlined below are the overall mass balance and stream properties. On the reactor-side of the process
only preliminary mass balances were performed since separation mass balances were calculated using
ASPEN simulations later in the design process. Microsoft EXCEL was used to make sure that the mass
balanced with the reactions and side products that were made in the overall reaction train. This EXCEL
sheet can be seen in Appendix C.
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V. Process Design Bains, Clark, Lowey, Soo
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Block (100)
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Name Form ul a MW (l b/l bmol) S-101 S-102 S-103 S-104 S-105 S-106 S-107 S-108 S-109 S-110
Oxygen O2 32 0 0 0 0 0 0 0 0 0 0
Hydrogen H2 2 0 0 0 0 0 0 0 0 0 0
Nitrogen N2 28 0 0 0 0 0 0 0 0 0 0
Ammonia NH3 17 0 0 2.00E-18 2.00E-18 2.00E-18 484.6719 484.6719 2.00E-18 2.00E-18 484.6719
Water H2O 18 0 0 0 0 0 0 0 0 0 0
Carbon Dioxide CO2 44 0 0 0 0 0 0 0 0 0 0
Niacinamide C6H6 N2O 122.1 0 0 0 0 0 0 0 0 0 0
Methylpentanediamine C6H16 N2 116.2 3306.93 3306.93 3340.33 3340.33 3340.33 33.40 0.00 33.40 33.40 0.00
Met hylpiperidine C6H13 N 99.2 0 0 3.13E-0 3 3.13E-0 3 3.13E- 03 2822 .2775 2822.2 744 3.13E-0 3 3.13E-0 3 2822. 2744
3-Met hylpyridine C6H7 N 93.1 0 0 0 0 0 0 0 0 0 0
3-Cyanopyridine C6H4 N2 104.1 0 0 0 0 0 0 0 0 0 0
3306.93 3306.93 3340.34 3340.34 3340.34 3340.35 3306.95 33.40 33.40 3306.95
Temperature (F) 77 77.373 81.1415 527 560.2087 581 266.2846 402.3192 402.6851 393.1779
Pressure (psia) 14.5038 43.5113 43.5113 33.5113 72.5189 71.6486 14.6959 20.5459 43.5113 72.5189
Vapor Fraction 0 0 0 1 1 1 1 1.23E-08 0 1
Liquid Fraction 1 1 1 0 0 0 0 1 1 0
Enthalpy (BTU/hr) -2.03E+06 -2.03E+06 -2.05E+06 -5.79E+05 -5.23E+05 -9.75E+05 -1.50E+06 -1.38E+04 -1.38E+04 -1.31E+06
Name Form ul a MW (l b/l bmol) S-111 S-112 S-113 S-114 S-115 S-116 S-117 S-118 S-119
Oxygen O2 32 0 0 0 0 0 0 0 0 0
Hydrogen H2 2 0 170.3884 170.3884 170.3884 170.3884 0 0 3.04E-14 1.55E-13
Nitrogen N2 28 0 0 0 0 0 0 0 0 0
Ammonia NH3 17 484.6719 484.6719 484.6719 484.6719 4.2846 0 0 480.3873 1.83E-06
Water H2O 18 0 0 0 0 8.94E-10 1200 1200 1200 0
Carbon Dioxide CO2 44 0 0 0 0 0 0 0 0 0
Niacinamide C6H6 N2O 122.1 0 0 0 0 0 0 0 0 0
Methylpentanediamine C6H16 N2 116.2 3.63E-03 3.63E-03 3.69E-17 3.69E-17 0 0 0 0 3.63E-03
Met hylpiperidine C6H13 N 99.2 2822 .2744 28.22 27 1.47E-0 4 1.47E-0 4 3.09E- 06 0 0 1.44E-0 4 28.222 6
3-Met hylpyridine C6H7 N 93.1 0 2623.8 311 1.414 8 1.414 8 7.03E- 06 0 0 1.414 8 2622. 41633-Cyanopyridine C6H4 N2 104.1 0 0 0 0 0 0 0 0 0
3306.95 3307.12 656.48 656.48 174.67 1200.00 1200.00 1681.80 2650.64
Temperature (F) 554 554 5.9902 313.672 -117.8784 90 90.9526 224.717 366.2599
Pressure (psia) 62.5189 42.2136 40 170 170 15 170 170 40
Vapor Fraction 1 1 1 1 1 0 0 5.12E-06 4.44E-07
Liquid Fraction 0 0 0 0 0 1 1 1 1
Enthalpy (BTU/hr) -1.02E+06 1.58E+06 -6.19E+05 -3.61E+05 -1.17E+05 -8.26E+06 -8.26E+06 -8.91E+06 1.08E+06
Flow Rate (lb/hr)
Block 100 (cont)
Total Mass Flow (lb/hr)
Total Mass Flow (lb/hr)
Flow Rate (lb/hr)
Block 100
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Block (200)
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Na me Fo rm ul a MW (l b/l bmol) S-201 S-202 S-203 S-203A S-204 S-205 S-206 S-206A S-207 S-208
Oxygen O2 32 0 0 0 0 1481.4509 135.6763 135.6763 135.6763 135.6763 135.42
Hydrogen H2 2 3.34E-16 3.00E-14 1.85E-13 1.85E-13 0 0 0 0 0 0
Nitro gen N2 28 0 0 0 0 0 0.3946 0.3946 0.3946 0.3946 0.3945
Ammonia NH3 17 5.2843 475.103 475.1031 475.1031 0 7.89E-02 7.89E-02 7.89E-02 7.89E-02 4.25E-03
Water H2O 18 13.2 1186.8 1186.8 1186.8 0 2696.0476 2696.0476 2696.0476 2198.5821 2.5583
Carbon Dioxide CO2 44 0 0 0 0 0 7.4396 7.4396 7.4396 7.4396 7.1777
Niacinamide C6H6 N2O 122.1 0 0 0 0 0 0 0 0 3372.1643 2.08E-04
Methylpentanediamine C6H16 N2 116.2 0 0 3.63E-03 3.63E-03 0 3.63E-03 3.63E-03 3.63E-03 3.63E-03 1.56E-04
Met hylpiperidine C6H13 N 99.2 1.58E- 06 1.42 E-04 28.22 27 28.22 27 0 28.22 27 28.22 27 28.2 227 28.22 27 2.03 83
3-Met hylpyridine C6H7 N 93.1 1.56E- 02 1.399 3 2623 .8156 2623 .8156 0 23.61 43 23.61 43 23.6 143 23.61 43 0.73 93
3-Cyanopyridine C6H4 N2 104.1 0 0 0 0 0 2903.918 2903.918 2903.918 29.0392 0.1032
18.50 1663.30 4313.95 4313.95 1481.45 5795.40 5795.40 5795.40 5795.22 148.44
Temperature (F) 224.717 224.717 626 158.8554 77 626 77 100 77 77
Pressure (psia) 170 170 30 40 39.4503 29.1298 19.1298 24.1298 14.7298 14.7298
Vapor Fraction 5.12E-06 5.1152E-06 1 0.060995 1 1 0.024904 0.025426 0.029574 1
Liquid Fraction 1 1 0 0.939 0 0 0.9751 0.9746 0.9704 0
Enthalpy (BTU/hr) -9.80E+04 -8.81E+06 -5.13E+06 -7.73E+06 -4.45E+02 -1.10E+07 -1.55E+06 -1.54E+07 -1.66E+07 -4.28E+04
Na me Fo rm ul a MW (l b/l bmol) S-209 S-210 S-211 S-212 S-213 S-214 S-215 S-216 S-217 S-218
Oxygen O2 32 135.42 0.2563 0.2563 135.6763 135.6763 135.6763 135.411 135.411 0.2654 0.2654
Hydrogen H2 2 0 0 0 0 0 0 0 0 0 0
Nitro gen N2 28 0.3945 8.58E-05 8.58E-05 0.3946 0.3946 0.3946 0.3945 0.3945 8.88E-05 8.88E-05
Ammonia NH3 17 4.25E-03 7.47E-02 7.47E-02 7.89E-02 7.89E-02 7.89E-02 4.12E-03 4.12E-03 7.48E-02 7.48E-02
Water H2O 18 2.5583 2196.0238 2196.0238 2198.5821 2198.5821 2198.5821 2.4717 2.4717 2196.1104 2196.1104
Carbon Dioxide CO2 44 7.1777 0.2619 0.2619 7.4396 7.4396 7.4396 7.1688 7.1688 0.2708 0.2708
Niacinamide C6H6 N2O 122.1 2.08E-04 3372.1641 3372.1641 3372.1643 3372.1643 3372.1643 2.01E-04 2.01E-04 3372.1641 3372.1641
Methylpentanediamine C6H16 N2 116.2 1.56E-04 3.47E-03 3.47E-03 3.63E-03 3.63E-03 3.63E-03 1.51E-04 1.51E-04 3.47E-03 3.47E-03
Met hylpiperidine C6H13 N 99.2 2.038 3 26.1 844 26.18 44 28.22 27 28.22 27 28.22 27 1.974 7 1.974 7 26.24 81 26.24 81
3-Met hylpyridine C6H7 N 93.1 0.739 3 22.87 5 22.87 5 23.61 43 23.61 43 23.61 43 0.715 3 0.715 3 22.89 91 22.89 91
3-Cyanopyridine C6H4 N2 104.1 0.1032 28.936 28.936 29.0392 29.0392 29.0392 9.98E-02 9.98E-02 28.9394 28.9394148.44 5646.78 5646.78 5795.22 5795.22 5795.22 148.24 148.24 5646.98 5646.98
Temperature (F) 249.416 77 77.1252 78.9689 77 77 77 228.908 77 77.1252
Pressure (psia) 31.8503 14.7298 29.7298 29.7298 19.7298 15.2298 15.2298 30.2298 15.2298 30.2298
Vapor Fraction 1 0 0 0.028952 0.029258 0.029534 1 1 0 0
Liquid Fraction 0 1 1 0.971 0.9707 0.9705 0 0 1 1
Enthalpy (BTU/hr) -3.69E+04 -1.66E+07 -1.66E+07 -1.66E+07 -1.66E+07 -1.66E+07 -4.22E+04 -3.71E+04 -1.66E+07 -1.66E+07
Flow Rate (lb/hr)
Flow Rate (lb/hr)
Block 200 (cont)
Total Mass Flow (lb/hr)
Total Mass Flow (lb/hr)
Block 200
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Block (200) (Streams continued)
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Nam e Formu la MW (l b/l bmol) S-219 S-220 S-221 S-222 S-223 S-224 S-225 S-226 S-227 S-228
Oxygen O2 32 135.6763 135.6763 135.6763 135.4019 135.4019 0.2744 0.2744 135.6763 135.6763 135.4641
Hydrogen H2 2 0 0 0 0 0 0 0 0 0 0
Nitrogen N2 28 0.3946 0.3946 0.3946 0.3945 0.3945 9.18E-05 9.18E-05 0.3946 0.3946 0.3946Ammonia NH3 17 7.89E-02 7.89E-02 7.89E-02 3.99E-03 3.99E-03 7.49E-02 7.49E-02 7.89E-02 7.89E-02 1.32E-03
Water H2O 18 2198.5821 2198.5821 2198.5821 2.3908 2.3908 2196.1913 2196.1913 2198.5821 2198.5821 0.4615
Carbon Dioxide CO2 44 7.4396 7.4396 7.4396 7.1599 7.1599 0.2797 0.2797 7.4396 7.4396 7.0928
Niacinamide C6H6 N2O 122.1 3372.1643 3372.1643 3372.1643 1.95E-04 1.95E-04 3372.1641 3372.1641 3372.1643 3372.1643 1.17E-05
Methylpentanediamine C6H16 N2 116.2 3.63E-03 3.63E-03 3.63E-03 1.46E-04 1.46E-04 3.48E-03 3.48E-03 3.63E-03 3.63E-03 6.52E-05
Met hylpiperidine C6H13 N 99.2 28.22 27 28.22 27 28.22 27 1.915 1.915 26.30 78 26.30 78 28.22 27 28.22 27 1.111 6
3-Met hylpyridine C6H7 N 93.1 23.61 43 23.61 43 23.61 43 0.692 7 0.692 7 22.92 16 22.92 16 23.61 43 23.61 43 0.327 5
3-Cyanopyridine C6H4 N2 104.1 29.0392 29.0392 29.0392 9.65E-02 9.65E-02 28.9426 28.9426 29.0392 29.0392 3.31E-02
5795.22 5795.22 5795.22 148.06 148.06 5647.16 5647.16 5795.22 5795.22 144.89
Temperature (F) 78.7705 77 77 77 275.3011 77 77.2505 79.3753 32 32
Pressure (psia) 30.2298 20.2298 15.7298 15.7298 37.7298 15.7298 45.7298 37.7298 27.7298 15
Vapor Fraction 0.028936 0.029234 0.029496 1 1 0 0 0.028787 0.028529 1
Liquid Fraction 0.9711 0.9708 0.9705 0 0 1 1 0.9712 0.9715 0
Enthalpy (BTU/hr) -1.66E+07 -1.66E+07 -1.66E+07 -4.17E+04 -3.50E+04 -1.66E+07 -1.66E+07 -1.66E+07 -1.68E+07 -3.16E+04
Nam e Formu la MW (l b/l bmol) S-229 S-230 S-231
Oxygen O2 32 0.2122 0.2122 0.2122
Hydrogen H2 2 0 0 0
Nitrogen N2 28 5.32E-05 5.32E-05 5.32E-05
Ammonia NH3 17 7.76E-02 7.76E-02 7.76E-02
Water H2O 18 2198.1206 2198.1206 2198.1206
Carbon Dioxide CO2 44 0.3468 0.3468 0.3468
Niacinamide C6H6 N2O 122.1 3372.1643 3372.1643 3372.1643
Methylpentanediamine C6H16 N2 116.2 3.56E-03 3.56E-03 3.56E-03
Met hylpiperidine C6H13 N 99.2 27.11 12 27.11 12 27.11 12
3-Met hylpyridine C6H7 N 93.1 23.28 69 23.28 69 23.28 69
3-Cyanopyridine C6H4 N2 104.1 29.0061 29.0061 29.0061
5 650 .33 56 50 .3 3 56 50 .3 3
Temperature (F) 32 32.2422 90
Pressure (psia) 15 45 35
Vapor Fraction 0 0 0
Liquid Fraction 1 1 1
Ent halpy (BT U/hr) -1.68E+07 -1.68E+07 -1.65E+07
Total Mass Flow (lb/hr)
Flow Rate (lb/hr)
Total Mass Flow (lb/hr)
Block 200 (cont) Flow Rate (lb/hr)
Block 200 (cont)
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Block (300)
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Nam e Formu la MW (l b/l bmol) S-301 S-302 S-304 S-305 S-306 S-307 S-308 S-309 S-310 S-311
Oxygen O2 32 0.2129 0.2129 0.2129 0.2129 0.2129 0.2129 0 0 2.1222 2.1222
Hydrogen H2 2 3.34E-16 3.34E-16 3.34E-16 0 0 0 0 0 0 0
Nitrogen N2 28 2.09E-03 2.09E-03 2.09E-03 2.09E-03 2.09E-03 2.09E-03 30.8796 30.8796 308.7963 308.7963
Ammonia NH3 17 53.5941 53.5941 53.5941 53.5941 53.5941 53.5941 0 0 53.6188 53.6188
Water H2O 18 2.21E+04 2.21E+04 2.21E+04 2.21E+04 2.21E+04 2.21E+04 0 0 2.21E+04 2.21E+04
Carbon Dioxide CO2 44 0.3659 0.3659 0.3659 0.3659 0.3659 0.3659 0 0 3.4681 3.4681
Niacinamide C6H6 N2O 122.1 3372.1643 3372.1643 3372.1643 3372.1643 3372.1643 3372.1643 0 0 0 0
Methylpentanediamine C6H16 N2 116.2 3.56E-03 3.56E-03 3.56E-03 3.56E-03 3.56E-03 3.56E-03 0 0 0 0
Met hylpiperidine C6H13 N 99.2 27.11 12 27.11 12 27.11 12 27.11 12 27.11 12 27.11 12 0 0 0 0
3-Met hylpyridine C6H7 N 93.1 23.30 24 23.30 24 23.30 24 23.30 24 23.30 24 23.30 24 0 0 0 0
3-Cyanopyridine C6H4 N2 104.1 29.0061 29.0061 29.0061 29.0061 29.0061 29.0061 0 0 0 0
25618.76 25618.76 25618.76 25618.76 25618.76 25618.76 30.88 30.88 22481.01 22481.01
Temperature (F) 30.9724 77 77.0265 77 76.9392 392 77 392 387.1028 887.2012
Pressure (psia) 35 25 20 15 39.9465 29.9465 29.5007 19.5007 14.5007 68.0082
Vapor Fraction 0.00034792 0.00026201 0.00030069 0.00035328 0 1 1 1 1 1
Liquid Fraction 0.9997 0.9997 0.9997 0.9996 1 0 0 0 0 0
Enthalpy (BTU/hr) -1.55E+08 -1.54E+08 -1.54E+08 -1.54E+08 -1.54E+08 -1.25E+08 -5.9364 2425.2806 -0.3685 -1.19E+08
Nam e Formu la MW (l b/l bmol) S-312 S-312A S-313 S-314 S-315 S-316 S-317 S-318 S-319
Oxygen O2 32 2.1222 2.1222 2.1214 0.2121 1.9093 0 7.50E-04 6.75E-04 7.50E-05
Hydrogen H2 2 0 0 0 0 0 0 0 0 0
Nitrogen N2 28 308.7963 308.7963 308.794 30.8794 277.9146 0 2.27E-03 2.04E-03 2.27E-04
Ammonia NH3 17 53.6188 53.6188 2.73E-02 2.73E-03 2.46E-02 0 53.5914 48.2323 5.3591
Water H2O 18 2.21E+04 2.21E+04 0.2025 2.03E-02 0.1823 0 2.21E+04 1.99E+04 2211.3003
Carbon Dioxide CO2 44 3.4681 3.4681 3.4469 0.3447 3.1022 0 2.12E-02 1.91E-02 2.12E-03
Niacinamide C6H6 N2O 122.1 0 0 0 0 0 3372.1643 0 0 0
Methylpentanediamine C6H16 N2 116.2 0 0 0 0 0 3.56E-03 0 0 0
Met hylpiperidine C6H13 N 99.2 0 0 0 0 0 27.11 12 0 0 0
3-Met hylpyridine C6H7 N 93.1 0 0 0 0 0 23.30 24 0 0 03-Cyanopyridine C6H4 N2 104.1 0 0 0 0 0 29.0061 0 0 0
22481.01 22481.01 314.59 31.46 283.13 3451.59 22166.62 19950.25 2216.66
Temperature (F) 32 100 32 31.6692 31.6692 387.1028 32 32.0274 32.0274
Pressure (psia) 58.0082 63.0082 58.0082 48.0082 48.0082 14.5007 58.0082 48.0082 48.0082
Vapor Fraction 0.009 0.0091 1 1 1 0 0 1 1
Liquid Fraction 0.991 0.9909 0 0 0 1 1 0 0
Enthalpy (BTU/hr) -1.54E+08 -1.52E+08 -1.81E+04 -1810.8 -1.63E+04 -1.17E+06 -1.54E+08 -1.38E+08 -1.54E+07
Flow Rate (lb/hr)
Block 300 (cont)
Total Mass Flow (lb/hr)
Block 300
Total Mass Flow (lb/hr)
Flow Rate (lb/hr)
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B. PROCESS DESCRIPTION
The proposed process is separated into three blocks. The first block (Block 100) involves the reaction
train in which MPDA is converted to PIC. The second block (Block 200) involves the reaction train in
which PIC is converted to the desired product: niacinamide. The last block (Block 300) includes the
purification and separation of the niacinamide to give the desired end product.
Block (100): Reaction Train 1 — MPDA to PIC
Summary
S-101 is the input for the process containing liquid MPDA. This stream undergoes a pressure increase and
is then passed through a heat exchanger where the MPDA is vaporized. The MPDA is then compressed
and passed through the first reactor. Reactor 1 converts the MPDA to methylpiperidine with a byproduct
of ammonia. More information about reactor 1 can be found in the Reactor Design section. The
distillation column that follows separates out the unreacted MPDA to be recycled back into the first
reactor while the remaining organic compounds and the ammonia continue through the process. The
stream is compressed again and fed into Reactor 2 which converts the methylpiperidine to 3-picoline with
a byproduct of hydrogen gas.
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Reactor Design
Reactor Train 1 (R-101)
The first step in the process is the cyclization/deamination of MPDA to form MPI and ammonia as a
byproduct. This takes place through a tubular reactor at temperatures and pressures in the range of 572 –
752°F and 0 – 145 psia respectively over activated Al2O3/SiO2 catalysts or zeolites. As the availability of
information regarding the kinetics of the reaction is greatly limited, the initial basis of the reactor’s design
was based on the patent by Lonza (Heveling et al., 1998) in which a range of reaction conditions and their
corresponding yields and conversions for a bench-scale set-up were documented. The optimal conditions
that gave the highest conversion for the first reaction were found to occur at 581°F at a pressure of 72.5
psia with a mass hourly space velocity (MHSV) of 4.2 lb/lb-hr over HZSM-5 catalysts. The composition
of HZSM-5 catalysts to be used is 54.5% of pentasil (Si/Al = 18) + 45.5% of binder.
For the design of Reactor Train 1, similar reactions
were researched to find the best reactor for the unit.
In drawing similarities between the first reaction in
the train and that of commercial naphtha reforming
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optimal at a temperature of 581°F, but the reaction is exothermic; therefore, the initial feed is sent through
four reactors, each in increasing size, with a cooling unit between each reactor to keep a relatively
constant temperature of 581°F. This allows the stream to stay within the range of optimal catalytic
selectivity, overall conversion, and minimal catalyst degradation. By using this design, a similar
conversion to that of what was expressed in the Lonza process with tubular reactors can be accomplished.
Within each of these reactors, H-ZSM-5 would be used as the heterogeneous catalyst.
Reactor Sizing
Approximately 3,340 lb/hr of MPDA vapor at 560°F and 72.5 psia is fed into the first reactor of Reactor
Train 1. When the MPDA vapor enters the first reactor, it reacts upon contact with the catalyst, increasing
the temperature. It should then pass through the cooling unit before entering the next reactor of the reactor
train, decreasing the reactor temperature. The resulting temperature profile would then have an
approximate saw-tooth appearance. Overall the average temperature is approximately 581°F.
Amount of Catalyst
The volume of catalyst required was calculated via scaling up from the patent to determine the amount
needed to convert 3 340 lb/hr of MPDA With a MHSV of 0 6 lb/lb-hr 5 600 lb of HZSM-5 catalyst were
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of 1 inch on each side. With a required catalyst volume of 224 ft 3, this gave the overall tube length of
10,270 ft. A nominal pipe size of 6 inches was chosen for the tube. To account for a more manageable
reactor length, fifteen tubes will be used, giving the length of one tube to be 685 ft, with the catalyst
support accounted for. Using 15 tubes, the volumetric flow rate through one tube then becomes 1,010
ft3/hr, thereby giving a superficial velocity of 3.6 ft/s through one tube, a reasonable velocity for vapor
through a tube to react. At these dimensions, the Reynolds number for flow through the tubes is small
enough that the reactants can approximate plug-flow conditions. Since the overall catalyst requirement is
224 ft3, the reactor length ratio for each of the four reactors should be, in increasing order, 68: 103: 171:
342 ft. In addition, a recycled loop may be added to the overall system to increase the percent conversion
of MPDA added into the system. In this manner, the reactor would be designed as a semi-regenerative
reactor unit with four reactors and a large cooling unit integrated into the process to cool the reaction
feeds since the overall reaction is exothermic (Askari, A., et al., 2012).
Pressure Drop
To estimate the pressure drop across the reactor, the Darcy – Weisbach equation was used. Operating at
72.5 psi at the above dimensions, the pressure drop across the tubes was 0.87 psi. The pressure is
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Reactor Train 2 (R-102)
The second step in the process is the endothermic dehydrogenation of MPI to PIC, producing hydrogen as
a byproduct. According to Lonza’s patent, the second reaction preferably takes place in a fixed-bed
reactor filled with noble metals as catalysts, such as Pd or Pt, on a support at 428 – 752°F and pressures of
0 – 145 psia. Again, based on the patent by Lonza (Heveling et al., 1998), the optimal conditions were
found to occur at 554°F at atmospheric pressure with 0.44 lb/lb-hr MHSV over 1% Pd-SiO2/Al2O3
catalysts.
Reactor 2 is also designed using a reaction similar
to one already present in commercial processing.
In the Fischer-Tropsch process, which converts
hydrogen and carbon monoxide to hydrocarbons,
multi-tubular reactors are used to aid in the steam
reforming piece of Fischer-Tropsch (Figure
4)(Elshout, R., 2010). In steam reforming, feed is
run through a series of packed bed reactor tubes,
which are heated by a fuel source or in this case, aFigure 4. Reformer Furnace Design. Source: “HydrogenProduction by Steam Reforming” Ray Elshout Chemical
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Amount of Catalyst
From S-111, approximately 3,310 lb/hr of material at 554°F at 40 psia is fed into Reactor 2 at 9,680 ft3/hr.
Stream S-111 primarily consists of approximately 0.15 mass% of ammonia and 0.85 mass% of MPI.
From the patent, the volume of catalyst required was calculated via scaling up to determine the amount
needed to convert 2,822 lb/hr of MPI. With a MHSV of 0.44 lb/lb-hr, 6,410 lb of 1% Pd-SiO 2/Al2O3
catalysts were required for the entire reactor train. Assuming a weighted catalyst density of 211 lb/ft
3
and
a void fraction of 0.5, the total volume of catalysts required would then be 60 ft3. The total price of the
catalyst is $ 783,300. Please reference page 236 for Sample Calculations.
Reactor Sizing
Based on the volume of catalyst required, the conventional Fischer-Tropsch reactor would need to be
scaled down to the following specifications: 40 tubes with a tube length of 20 ft and a diameter of 4
inches.
Pressure Drop
To estimate the pressure drop across the reactor, the Ergun equation for packed bed was used. The
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Process Modeling
To model the first block of the process, ASPEN V 7.3.1 was used. However, due to the complexity of the
process, some simplifications and assumptions were made to use ASPEN to simulate the overall process.
It is known that a separation column was used in Lonza’s process to separate and divert the unreacted
MPDA to be recycled back to the first reactor (ICIS.com, 1999). It is assumed that this separation unit
was a distillation column. In ASPEN, this distillation column was modeled using RADFRAC, which did
a relatively good job of calculating the energy and tray requirements for the separation. Additionally,
there were two absorbers added to the process to help separate hydrogen from the system after the second
reactor; by removing this stream, the hydrogen can be fed to a Dowtherm system as fuel, whereas the
remainder of the units in the process could also be decreased in size due to the absence of hydrogen. In
ASPEN, these two absorbers were modeled using the ABSRB1 and ABSRB2 subroutine under the
RADFRAC unit, respectively. The second absorbing column, A-102, was used with water as the
absorbing agent because ammonia dissolves readily in this solvent, leaving hydrogen in the other stream
to be used later as a fuel.
Block (200): Reaction Train 2 — PIC to Niacinamide
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stream then continues to a two-stage heat exchanger to cool to more moderate operating conditions
needed for the biocatalyst reactors. After this stream is cooled, it enters a CSTR reactor that contains the
biocatalyst necessary to react 3-cyanopyridine with water to make niacinamide. The vapor and liquid
streams from this reactor are moved by blowers and compressors, respectively, to the next reactor. This
occurs for three CSTRs in series; three CSTRs in series not only increase the conversion but also allows
for a longer residence time in each of the reactors.
After the final CSTR, stream S-226 is cooled down to help separate the vapor products present in the
stream before the organic trace materials and the niacinamide continues to the third block in the process.
S-228, the waste stream from the flash vessel, contains mostly oxygen, hydrogen, and water vapor. Some
trace organics are present in this stream including CNP, PIC, and MPI. However, this stream will later be
cleansed of these contaminants. Before being transferred to the third block, the stream containing mostly
organics and water is heated and mixed in M-301 with the remainder of the ammonia and water mixture
taken from the splitter in Block 100.
Reactor Design
Reactor Train 3
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Reactor 3 is designed as a multitubular reactor as used in the Fischer-Tropsch synthesis. In the same
manner as Reactor 2, a steam reforming reactor design can be implemented to increase the yield of the
reaction. However, instead of using the Dowtherm to heat the reaction, a cooling fluid would flow
through the reactor to decrease the temperature as necessary throughout the reactor. This reactor
comprises a single shell compartment with 2,000 tubes filled with catalysts in the form of rings. Each
individual tube will have an internal diameter of 1.8 in and a length of 42 ft as scaled up from Modeling of
Multi-Tubular Reactors for Fischer-Tropsch Synthesis (Jess & Kern, 2009). The overall reactor geometry
is similar to that of conventional shell-and-tube type heat exchangers, but with no tube zone in the center
of the reactor. The reacting gas enters at the bottom of the unit. The optimal conditions are at 626°F and
atmospheric pressure, with catalysts consisting of V2O5, TiO2, ZrO2, and MoO3.
Amount of Catalyst
From S-203, approximately 4,314 lb/hr of material at 626°F at 30 psia is fed into Reactor 3 at 47,200
ft3/hr. Stream S-203 primarily consists of approximately 0.11 mass% of ammonia, 0.28 mass% of water,
and 0.61 mass% of PIC. From the patent, the volume of catalyst required was calculated via scaling up to
determine the amount needed to convert 2,624 lb/hr of PIC. With a MHSV of 5.24 lb PIC/ft 3 catalyst-hr,
3
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Pressure Drop
To estimate the pressure drop across the reactor, the Darcy – Weisbach equation was used. At the reactor
dimensions, the pressure drop across the tubes was 0.87 psi. The pressure is relatively small since it is a
homogeneous tubular reactor. Since the pressure remains relatively constant throughout the process;
therefore, there should be no issues in significant pressure drop.
Heat Transfer Requirements
With a heat duty of -5.88 MMBtu/hr, it was determined that 196,694 lb/hr of cooling water was required
as a cooling utility to attain and maintain the operating temperature conditions. The overall heat transfer
coefficient is set at 60 Btu/lb-hr-°F as per consultants’ (Mr. Wismer and Mr. Kolesar) suggestion.
Reactor Train 4
The fourth step in the process is the enzymatic hydrolysis of 3-cyanopyridine to niacinamide in a
continuous feed batch reactor cascade comprising of 2 – 5 connected stirred reactors, catalyzed by an
enzyme produced by microorganisms of the species Rhodococcus rhodochrous J1, which is immobilized,
over temperatures of 41 – 122°F at atmospheric pressure. According to the Lonza patent (Heveling et al.,
1998) the process is best carried out at ambient temperature and pressure using the species Rhodococcus
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Reactor Train 4 is designed as adiabatic, stirred-tank reactors using immobilized whole cells of R.
rhodochrous J1 employed in three stages. Sizing of the reactor was done via scaling up of the bench-scale
data from the Lonza patent. It was determined that the three reactor tanks for Reactor 4 (R-202A, R-202B,
and R-202C) will each have a carbon steel construction, an agitation rate of 110 rpm, a volume of 6,975
ft3, and will be operating at room temperature and pressure. The residence time of the whole cascade will
be 12 hours, with 4 hours for each vessel (Nagasawa et al., 1988).
Mass of Biocatalyst
The dry weight of whole cell biocatalyst R. rhodochrous J1 immobilized in polyacrylamide particles was
calculated via scaling up of the bench-scale data from the patent. It was determined that each 6,975 ft3
tank would house 1,740 lb (dry weight) of the whole cell biocatalyst R. rhodochrous J1 immobilized in
polyacrylamide particles. This is equivalent to 878.7 lb of immobilized enzyme, nitrile hydratase, NHase.
The cell density of each reactor would then be 0.25 lb/ft3. The total price of the catalyst is $153,910 for all
three vessels. Refer to page 237 for Sample Calculations.
Cascade Choice
In terms of the cascade choice Lonza investigated several process options including single-stage
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for larger-scale operations, has the advantage of operating at a low substrate level, and is suitable for
substrate-inhibition reactions.
Agitator
The agitation rate in the reactors will be limited at 110 rpm to not disturb cell growth profiles and prevent
cell membrane damage as high agitation rates can shear the cells. Furthermore, research has shown that
specific product formation for bioprocesses is generally higher at lower impeller speeds (Doble, 2006).
Two pitched blade turbines as agitators would be required for each vessel, each operating at 35 hp.
Process Modeli ng
Another set of simplifications occurred when dealing with the reaction vessels. Since specifications were
not given on any of the first three reactors, they were modeled using the RSTOIC block in ASPEN. These
reactors had the respective reactions added into them, assuming a certain conversion of the reaction. For
the side reactions that may occur in the process, the third reactor, R-201, had a fraction of the 3-
methylpyridine that is produced in that reactor essentially combust and form nitrogen, carbon dioxide, and
water. This effectively accounts for the product lost in the process as well as the energy associated with
these side products in the third reactor.
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move the vapor stream. Heat exchangers were placed after the pump and blower before entering into the
next reaction vessel.
Block (300): Niacinaide Purification
Summary
The third block in the process models the purification of niacin. After M-301 mixes the ammonia and
water stream from A-102 earlier with the recycled stream of ammonia and water, the remainder of the
organic molecules from the previous block mixes in as well. From the mixer, the stream goes to a heat
exchanger where the temperature of the stream is brought down to close to room temperature. The stream
enters the decolorizing unit, where the red dye leftover from the biocatalyst in the fourth reactor is
removed with activated carbon. This stream then travels to the neutralizer where a mixture of ammonia
and ammonium chloride create a buffer solution that effectively neutralizes the niacinamide formed in
previous stages. Following this step, the stream is increased in pressure with a pump and then heated up
to mix with the nitrogen streams coming in. Stream S-305 is heated nitrogen coming in to act as a drying
agent in the dryer. This nitrogen stream is heated before continuing to the bottom of the dryer, effectively
removing all the water and ammonia in the stream. The organic products, including the desired product
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Special ized Equipment
Decolorizing Unit
R. rhodochrous J1 has a red pigment (DiCosimo, R., 2006). The decolorizing unit is required to remove
the red pigment leftover from the biocatalyst in the fourth reactor. As such, the patent entitled Method for
purifying amide compounds by reacting with activated carbon under acidic conditions is referred to when
designing the column filled with activated carbon (Abe, T., et al., 2001). The unit is essentially an
adsorption column, modeled as a vertical pressure vessel, and is filled with activated carbon. Correlations
from Product and Process Design Principles were used to size and cost the entire unit — column and
activated carbon. Knowing the volumetric flow rate to be 7.74 ft 3/min and assuming a 10 minute
residence time in the column, the volume of material in the vessel is calculated to be 77 ft3
. Adjusting the
volume for potential dissolved vapor, sufficient volume occupied by the catalyst, and increases in
production capacity, the vessel volume is now 199 ft3, and is thus sized as 4 ft in diameter and 16 ft in
length. Void fraction of activated carbon is approximately 0.6. With this, the volume of activated carbon
required is calculated and cost as shown in Sample Calculations page 239.
Dryer
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scaled-up using information obtained from examples of performance data given in Perry’s and is
presented in Table B1 below (Perry & Green, 2008).
Table B1. Wyssmont TURBO-DRYER® performance data
Material Dried Niacinamide
Dried Product (lb/hr) 3372
Evaporation Rate (lb/hr) 650
Type of heating system Steam
Heating medium Hot gas
Drying medium Inert gas
Materials of Construction Stainless-steel interior
Dryer height (ft) 23
Dryer diameter (ft) 20
Recovery system Shell-and-tube condenser
Condenser cooling medium Chilled water
Location Indoor
Purchase Cost $ 804,369
Dryer assembly Packaged unit
Process Modeli ng
A decolorizer filled with activated carbon is needed for the third block of the process. However, ASPEN
Figure 5. Wyssmont Turbo-Dryer;
Source: Wyssmont Advertisement.
Chemical Engineering, Access
Intelligence. May 2010
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reaction are already satisfied with the water and ammonia already created in the overall process. This
made sure that the process would, under the right pH conditions, form the salt ammonium nicotinate,
effectively neutralizing the solution.
Finally, the dryer was modeled in ASPEN as a SEP block unit. Since the dryer block in ASPEN was
unable to work with this particular process design, a series of trial and error simulations were done to find
the best unit within ASPEN to model the dryer. After the dryer specific model in ASPEN did not
converge, a hierarchy block was added to convert the organic compounds previously defined as
conventional components to solids. Then, when the dryer still did not converge, the same was done with a
flash vessel. However, the separation in the flash vessel did not correctly model the dryer since most of
these components turned into liquids rather than solids when the necessary temperatures were reached,
around 387°F, whereas these components would be solids and fall out of the evaporated water and
ammonia in actuality. For rough estimates of purity and solid niacin chemical composition, a SEP unit
was finally decided to most accurately model the conditions and separation fractions of a dryer. All
organics in the stream leave as stream S-316 while the water, ammonia, and nitrogen are evaporated to
leave from the top of the vessel. The hot nitrogen mixture that enters through the bottom of the dryer
evaporates water and ammonia leaving behind the remainder of the organics; this SEP unit, as compared
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C.
EQUIPMENT LIST AND UNIT DESCRIPTIONS
Block (100)
Table C1. A list of equipment used in the process for Block (100).
Unit #Equipment
TypeFunction
Operating
T (°F)
Operating
P (psia)
A-101 AbsorberSeparates mainly H2 and NH3 from vaporstream (S-112) into S-113
C = 6R = 366
40
A-102 AbsorberSeparates mainly H2 from S-114 to S-115 via extraction with water in S-117
C = -118R = 225
170
C-101 CompressorIncreases pressure of S-104 beforerunning through R-101
560ΔP=39DischargeP = 73
C-102 CompressorIncrease pressure of distillate (S-107) ofD-101 before feeding it to R-102
393ΔP=58 DischargeP = 73
C-103 CompressorIncrease pressure of S-113 before runningthrough A-102
314ΔP=130 Discharge
P = 170D-101
DistillationColumn
Separate MPDA from S-106 to berecycled
D = 266B = 379
15
HX-101 Heat ExchangerIncreases temperature of S-103 for feedinto R-101
527 34
HX-102 Heat ExchangerIncreases temperature of S-110 for feedinto R-102
554 63
M-101 MixerMixes streams S-102 and S-109 for feedinto HX-101
81 44
P-101 PumpPumps S-101 to then run through HX-101 for MPDA vaporization
77ΔP=29 DischargeP = 44
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Absorber (A-101)
A-101 is a 20-stage column for separating mainly the hydrogen and ammonia from vapor stream S-112
into S-113. The inlet stream enters at Stage 17. Temperature varies in the column from 266°F in the
condenser (top stage) to 402°F in the reboiler (bottom stage).
The condenser is a partial-vapor fixed tube sheet heat exchanger that decreases the temperature of the
overhead before sending it through a compressor (C-103). The hot stream on the shell side is cooled from
274°F (Stage 2) to 6°F (Stage 1/S-113). 6,411,900 lb/hr of refrigerant, R-134a, enters the tube side to cool
the streams. The tube and shell side heat transfer coefficients are 250 and 2,632 Btu/hr-ft2-°F respectively,
leading to a total heat transfer area of 226 ft2. The total heat duty is -2.8 MMBtu/hr. There are 44 tubes of
20 ft. with an outer diameter of 1 in. The shell is 20 ft. in length and has a diameter of 10 in. with 16
baffles. With a carbon steel construction, the total bare-module cost of the condenser is $65,870.
The reboiler is a U-tube kettle vaporizer that uses high-pressure steam to vaporize a portion of the liquid
bottoms product of the column. The distillate on the tube side is heated from 366°F (Stage 20) to 444°F.
1,401 lb/hr of steam at 450 psia enters the shell side to heat the cold streams. The tube and shell side heat
transfer coefficients are 1,000 and 200 Btu/hr-ft2-°F respectively, leading to a total heat transfer area of
2
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Absorber (A-102)
A-102 is a 10-stage column for separating mainly hydrogen from S-114 to S-115 via extraction with
water in S-117. The inlet stream S-114 enters at Stage 8 while the inlet stream S-117 enters at Stage 2.
Temperature varies in the column from -118°F in the condenser (top stage) to 225°F in the reboiler
(bottom stage). The column manages to remove all of the hydrogen and recovers >99% by mass of the
ammonia in the inlet stream.
The condenser is a partial-vapor fixed tube sheet heat exchanger that decreases the temperature of the
overhead before sending it through a compressor (C-103). It has a reflux ratio of 1. The hot stream on the
shell side is cooled from 90°F (Stage 2) to -118°F (Stage 1/S-115). 2,799,830 lb/hr of refrigerant,
ethylene, enters the tube side to cool the streams. The tube and shell side heat transfer coefficients are 250
and 1,019 Btu/hr-ft2-°F respectively, leading to a total heat transfer area of 177 ft2. The total heat duty is -
1.2 MMBtu/hr. There are 34 tubes of 20 ft. with an outer diameter of 1 in. The shell is 20 ft. in length and
has a diameter of 10 in. with 16 baffles. With a carbon steel construction, the total bare-module cost of the
condenser is $73,300.
The reboiler is a U-tube kettle vaporizer that uses high-pressure steam to vaporize a portion of the liquid
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ASPEN Process Economic Analyzer (IPE). Please refer to the Absorber (A-102) specification sheet on
page 67 and in Appendix IX on page 241.
Compressor (C-101)
C-101 is a rotary twin-screw compressor used to increase the pressure of the vapor stream S-104 by 39 psi,
from 33.5 psia to 72.5 psia in S-105 before it is sent to the first reactor (R-101). The inlet volumetric flow
rate is 144 ft3/min. The power consumption of the unit is 25.3 HP. The compressor is powered using an
electric motor drive that consumes 17 kW. With a cast-iron construction, the total bare-module cost of the
unit is $86,720. Please refer to the Compressor (C-101) specification sheet on page 73 and the Sample
Calculations in Appendix IX on page 248.
Compressor (C-102)
C-102 is a rotary twin-screw compressor used to increase the pressure of the vapor stream S-107 by 57.8
psi, from 14.7 psia to 72.5 psia in S-110 before it is sent to the heat exchanger (HX-102) to be heated. The
inlet volumetric flow rate is 495 ft3/min. The power consumption of the unit is 81.6 HP. The compressor
is powered using an electric motor drive that consumes 55 kW. With a cast-iron construction, the total
bare-module cost of the unit is $202,400. Please refer to the Compressor (C-102) specification sheet on
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Distil lation Column (D-101)
D-101 is a 40-stage column for separating out the leftover MPDA from S-106 to be recycled back through
S-108. The inlet stream enters at Stage 33. Temperature varies in the column from 266°F in the condenser
(top stage) to 402°F in the reboiler (bottom stage). The column recovers >99.9% by mass of the MPDA in
the inlet stream. The number of stages required for the distillation column was obtained through ASPEN
simulations. A purity for MPDA removal was specified and operating conditions for the column were
optimized within ASPEN.
The condenser is a partial-vapor fixed tube sheet heat exchanger that decreases the temperature of the
overhead before sending it through a compressor (C-102). The hot stream on the shell side is cooled from
306°F (Stage 2) to 266°F (Stage 1/S-107). 231,890 lb/hr of cooling water enters the tube side to cool the
streams. The total heat duty is -6.9 MMBtu/hr. There are 52 tubes of 20 ft. with an outer diameter of 1 in.
The shell is 20 ft. in length and has a diameter of 12 in. with 16 baffles. With a carbon steel construction,
the total bare-module cost of the condenser is $59,060.
The reboiler is a U-tube kettle vaporizer that uses high-pressure steam to vaporize a portion of the liquid
bottoms product of the distillation column. The distillate on the tube side is heated from 318°F (Stage 40)
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Heat Exchanger (H X-101)
HX-101 is a floating head shell-and-tube heat exchanger that models an evaporator that increases the
temperature of the stream entering the first reactor R-101. S-103 on the tube side is heated from 81°F (S-
103) to 527°F (S-104). 5,872 lb/hr of Dowtherm A enters the shell side to heat the streams. The tube and
shell side heat transfer coefficients are 200 and 175 Btu/hr-ft2-°F respectively, leading to a total heat
transfer area of 143 ft2. The total heat duty is 1.5 MMBtu/hr. There are 27 tubes of 20 ft. with an outer
diameter of 1 in. The shell is 22 ft. in length and has a diameter of 10 in. with 18 baffles. With a carbon
steel construction, the total bare-module cost of the unit is $243,000. All calculations were performed
using ASPEN Plus Exchanger Design and Rating (EDR) and cost using ASPEN Process Economic
Analyzer (IPE). Please refer to the Heat Exchanger (HX-101) specification sheet on page 83 in Appendix
IX on page 250.
Heat Exchanger (H X-102)
HX-102 is a floating head shell-and-tube heat exchanger that increases the temperature of the stream
entering the second reactor R-102. S-110 on the tube side is heated from 393°F (S-110) to 554°F (S-111).
1,172 lb/hr of Dowtherm A enters the shell side to heat the streams. The tube and shell side heat transfer
coefficients are 100 and 175 Btu/hr-ft2-°F respectively, leading to a total heat transfer area of 104 ft2. The
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construction, the total bare-module cost of the unit is $100,806. Please refer to the Centrifugal Pump (P-
101) specification sheet on page 98 and the Sample Calculations in Appendix IX on page 252.
Pump (P-102)
P-102 is a centrifugal pump used to pump the bottoms from distillation column D-101 through stream S-
108 to S-109 to the mixer (M-101) to be recycled. For a pressure change of 23 psi, the head developed is
67 ft, and the net work required is 0.0038 HP. With a carbon steel construction, the total bare-module cost
of the unit is $100,426. Please refer to the Centrifugal Pump (P-102) specification sheet on page 99 and
the Sample Calculations in Appendix IX on page 252.
Pump (P-103)
P-103 is a centrifugal pump used to pump water through S-116 to the absorber (A-102) to absorb the
ammonia incoming from S-114. For a pressure change of 155 psi, the head developed is 362 ft, and the
net work required is 0.74 HP. With a carbon steel construction, the total bare-module cost of the unit is
$138,090. Please refer to the Centrifugal Pump (P-103) specification sheet on page 100 and the Sample
Calculations in Appendix IX on page 252.
Reactor 1 – Tubular Reactor (R-101)
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Reactor 2 – Packed Bed Reactor (R-102)
In Reactor 2, the MPI produced in R-101 is converted to PIC at an overall conversion of 99% in an
endothermic dehydrogenation reaction. Aforementioned this conversion is idealized; this conversion was
only used because it is based on the experimental data given from the bench scale experiments for the
process. R-102 is comprised of 40 tubes 20 ft in total length and nominal diameters of 4 inches, operating
at 554°F and a pressure of 42 psia over 1% Pd-SiO2/Al2O3 catalysts. With a stainless steel shell-and-tube
heat exchanger construction, the total heat transfer surface area is 838 ft2. The total bare-module cost of
the unit is $97,360. Please refer to the Reactor 2 (R-102) specification sheet on page 107.
Feed Storage Tank (T-101)
T-101 is a floating roof storage tank that stores the liquid MPDA feed at ambient temperature and
pressure. The tank has a storage capacity of 113,000 gallons of MPDA with a residence time of 7 days.
MPDA is fed continuously from the tank to the system via S-101. The choice of the floating-roof tank is
in compliance with current EPA regulations that dictate its usage for when, at the maximum atmospheric
temperature at the plant site, the vapor pressure of the liquid is greater than 0.75 psia for storage of more
than 40,000 gal. In our case, the vapor pressure is 2.5 psi at 275°F for 77,000 gallons. Using a cast-iron
construction, the total bare-module cost of the unit is $629,610. Please refer to the Feed Storage Tank
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Block (200)
Table C2. A list of equipment used in the process for the 200 block.
Unit # Equipment Type Function Operating
T (°F)
Operating
P (psi)
B-201 BlowerIncreases pressure of S-208 beforerunning through R-202B
251ΔP=17 DischargeP = 32
B-202 BlowerIncreases pressure of S-215 beforerunning through R-202C
230ΔP=15 DischargeP = 30
B-203 BlowerIncreases pressure of S-220 beforerunning through F-201
276ΔP=22 DischargeP = 38
F-201 Flash VesselInitial separation of organiccompounds from vapor products in S-227
32 15
HX-201 Heat ExchangerIncreases temperature of streams fedinto R-201
626 30
HX-202A Heat Exchanger Decreases temperature of S-205 forfeed into R-202A
100 19
HX-202B Heat ExchangerDecreases temperature of S-205 forfeed into R-202A
77 19
HX-203 Heat ExchangerDecreases temperature of S-212 before running through R-202B
77 20
HX-204 Heat ExchangerDecreases temperature of S-219 before running through R-202C
77 20
HX-205 Heat Exchanger Decreases temperature of S-226 before running through F-201 32 28
HX-206 Heat ExchangerIncreases temperature of S-230 beforebeing fed into M-301
90 35
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Unit # Equipment Type Function Operating
T (°F)
Operating
P (psi)
P-204 Pump Increases pressure of S-229 beforerunning through HX-206
32
ΔP=30
DischargeP = 45
R-201 Tubular ReactorConverts 3-picoline to 3-cyanopyridine and water
626 29
R-202ASemi-continuousstirred tank reactor
Converts 3-cyanopyridine toniacinamide (niacin)
77 15
R-202BSemi-continuousstirred tank reactor
Converts 3-cyanopyridine toniacinamide (niacin)
77 15
R-202C Semi-continuousstirred tank reactor
Converts 3-cyanopyridine toniacinamide (niacin)
77 16
SP-201 SplitterModels the control valves used tosplit the flow of S-118
225 170
Blower (B -201)
B-201 is a centrifugal blower used to increase the pressure of the vapor stream S-208 by 17.3 psi, from
14.6 psia to 31.9 psia in S-209 before it is sent to the heat exchanger HX-203 to be slightly cooled. The
power consumption of the unit is 2.8 HP. With a cast-iron construction, the total bare-module cost of the
unit is $5,490. Please refer to the Blower (B-201) specification sheet on page 70 and the Sample
Calculations in Appendix IX on page 247.
Blower (B -202)
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$6,080. Please refer to the Blower (B-203) specification sheet on page 72 and the Sample Calculations in
Appendix IX on page 247.
Flash Vessel (F-201)
F-201 is a vertical flash vessel for the separation of organic compounds from vapor products (mainly O 2)
in S-227. The unit operates at 32°F and 15 psia with a residence time of 5 minutes. The height and
diameter of the vessel is 12 and 3 ft respectively. With a steel (ASTM A516) construction, the total bare-
module cost of the unit is $535,640. Please refer to the Flash Vessel (F-201) specification sheet on page
81 and the Sample Calculations in Appendix IX on page 249.
Heat Exchanger (H X-201)
HX-201 is a floating head shell-and-tube heat exchanger that increases the temperature of the stream
entering the third reactor R-201. S-203 on the tube side is heated from 159°F (S-203A) to 626°F (S-203).
10,400 lb/hr of Dowtherm A enters the shell side to heat the streams. The tube and shell side heat transfer
coefficients are 200 and 143 Btu/hr-ft2-°F respectively, leading to a total heat transfer area of 209 ft 2. The
total heat duty is 2.6 MMBtu/hr. There are 40 tubes of 20 ft. with an outer diameter of 1 in. The shell is
22 ft. in length and has a diameter of 10 in. with 18 baffles. With a carbon steel construction, the total
$
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There are 28 tubes of 20 ft. with an outer diameter of 1 in. The shell is 22 ft. in length and has a diameter
of 10 in. with 18 baffles. With a carbon steel construction, the total bare-module cost of the unit is
$330,700. All calculations were performed using ASPEN Plus Exchanger Design and Rating (EDR) and
cost using ASPEN Process Economic Analyzer (IPE). Please refer to the Heat Exchanger (HX-202A)
specification sheet on page 86 in Appendix IX on page 250.
Heat Exchanger (HX-202B)
HX-202B is a floating head shell-and-tube heat exchanger that again models a partial condenser that
further decreases the temperature of the stream entering the first vessel of reaction train 4 (R-202A). The
hot stream on the shell side is cooled from 100°F (S-206A) to 77°F (S-206). 2,170,000 lb/hr of refrigerant
enters the tube side to cool the streams. The tube and shell side heat transfer coefficients are 1,050 and
470 Btu/hr-ft2-°F respectively, leading to a total heat transfer area of 224 ft2. The total heat duty is -
95,180 Btu/hr. There are 43 tubes of 20 ft. with an outer diameter of 1 in. The shell is 22 ft. in length and
has a diameter of 12 in. with 18 baffles. With a carbon steel construction, the total bare-module cost of the
unit is $244,500. All calculations were performed using ASPEN Plus Exchanger Design and Rating (EDR)
and cost using ASPEN Process Economic Analyzer (IPE). Please refer to the Heat Exchanger (HX-202B)
specification sheet on page 87 in Appendix IX on page 250.
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Heat Exchanger (H X-206)
HX-206 is a floating head shell-and-tube heat exchanger that increases the temperature of the bottoms
leaving the vapor liquid separator (F-201). S-230 on the tube side is heated from 32°F (S-230) to 90°F (S-
231). 185 lb/hr of hot water at 100°F enters the shell side to heat the streams. The tube and shell side heat
transfer coefficients are 1,000 and 303 Btu/hr-ft2-°F respectively, leading to a total heat transfer area of 6
ft2. The total heat duty is 223,490 Btu/hr. There is one 20 ft. tube with an outer diameter of 1 in. The shell
is 22 ft. in length and has a diameter of 3 in. with 18 baffles. With a carbon steel construction, the total
bare-module cost of the unit is $169,200. All calculations were performed using ASPEN Plus Exchanger
Design and Rating (EDR) and cost using ASPEN Process Economic Analyzer (IPE). Please refer to the
Heat Exchanger (HX-206) specification sheet on page 91 in Appendix IX on page 250.
Pump (P-201)
P-201 is a centrifugal pump used to pump liquid stream S-210 to be mixed, cooled, and sent to the second
reactor in the cascade of reaction train 4. For a pressure change of 15 psi, the head developed is 29 ft, and
the net work required is 0.28 hp. With a carbon steel construction, the total bare-module cost of the unit is
$113,740. Please refer to the Centrifugal Pump (P-201) specification sheet on page 101 and the Sample
Calculations in Appendix IX on page 252.
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Pump (P-203)
P-203 is a centrifugal pump used to pump liquid stream S-224 to be mixed, cooled, and sent to the vapor
liquid separator (F-201). For a pressure change of 30 psi, the head developed is 58 ft, and the net work
required is 0.56 hp. With a carbon steel construction, the total bare-module cost of the unit is $113,740.
Please refer to the Centrifugal Pump (P-203) specification sheet on page 103 and the Sample Calculations
in Appendix IX on page 252.
Pump (P-204)
P-204 is a centrifugal pump used to pump liquid stream S-229 to be heated through by the heat exchanger
(HX-206). For a pressure change of 30 psi, the head developed is 57 ft, and the net work required is 0.55
hp. With a carbon steel construction, the total bare-module cost of the unit is $103,090. This pump has the
same specifications as P-203. Therefore, two of the same pumps can be purchased for P-203 and P-204.
Please refer to the Centrifugal Pump (P-204) specification sheet on page 104 and the Sample Calculations
in Appendix IX on page 252.
Reactor 3 (R-201)
In the third reactor, the exothermic ammoxidation to produce 3-cyanopyridines (and water as a byproduct)
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Reactor 4 (R-202A,B,C)
In Reactor 4, the biohydrolysis of 3-cyanopyridine produces niacinamide and water as a byproduct with
an overall conversion of 99%. R-202A is the first in a series of three stirred-tank semi-batch reactors with
a continuous feed of 3-cyanopyridine via S-206 at concentrations of between 10 – 20 wt% in the direction
of process flow. The reactor also houses the whole cell biocatalyst R. rhodochrous J1 immobilized in
polyacrylamide particles. The enzymatic hydration produces the desired amide at >99.3% selectivity at
100% conversion. The reactors have a volume of 6,975 ft3 each and a residence time of 4 hours each, and
will operate at 77°F and 15 psia. Each vessel will be equipped with two turbine agitators with an agitation
rate of 110 rpm for each impeller. With a carbon steel (SA-285 Grade C) construction, the total bare-
module cost of one unit is $918,160 making the total bare-module cost of the entire cascade to be
$2,754,480. Please refer to the Stirred Tank Reactor specification sheet on page 109 and the Sample
Calculations in Appendix IX on page 253.
V P D i B i Cl k L S
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Block (300)
Table C3. A list of equipment used in the process for the 300 block.
Unit # Equipment Type Function Operating
T (°F)
Operating
P (psi)
AS-301Packed Bed AirStripper
Removes NH3 from S-319 so that theexcess water can be release to surroundings
6815
C-301 CompressorIncreases pressure of S-310 before enteringHX-304
887ΔP=54 DischargeP=68
DC-301 Decolorizing UnitRemoved red dye leftover from biocatalyst
in R-20277
20
DR-301 DryerAllows heated nitrogen to separate themixture in S-307 to product in S-316 andrecycled S-310
38715
F-301 Flash VesselSeparate N2 for recycle to the dryer;remainder to stream to liquid recycle, feedis S-312
3258
HX-301 Heat ExchangerIncreases temperature of S